PH26581A - Phenolic resin compositions - Google Patents

Description

Co, Co

This invention relates to phenolic resins.

More particularly, it relates to a method of mak=~. ing phenolic resin compositions from esterified phenolic compounds which produce said resin compos : 5 sitions on treatment with alkaline substances. The phenolic resin compositions produced from these esterified phenolic compounds under alkaline cons ditions have a reduced content of unreactive by~ products.

It is known that alkaline phenolic resins } may be cured under alkaline conditions through re=- action with organic esters, including lactones and organic carbonates. Such ester curing of alkaline phenolic resole resins is described, inter in DE~C

No. 1,065,605, DE=-C No. 1,171 ,6064 Jp=A Noe. 49s 16793, Jp=A Noo 50-130627, GB=A No. 2059973, EP~A

No. 0085512 and EP-A No. 0086615. According to these publications, a highly alkaline phenolic resole resin in aqueous solution may be cured at ambient temperature by reaction with an organic ester (ine ¢luding lactones and carbonates) by contacting the - resin with the ester in the form of a liquid or a gas.

Such resins find application particularly in the bonding of refractory materials, such as Band,

v s } ’ in the production of foundry moulds and cores and in treating subterranean formations. Other appli cations of the resin, such as in wood bonding, have alse been proposed.

The setting of highly. alkaline phenolic re~ gins with esters involves the saponification of the ester, but it is a disadvantage with the products heretofore produced that some products of the sapow= niftcation reaction are not incorporated into the final resin structure but remain in the cured mass : - as non@resinous compounds, in the form of free ale Co “cohel and in the form of the salt of the acid come | ~ pe Eee ghfient of the ester! Wille this is Hot i Serious! tm. ini ism At a so : | disadvantage in some of the applications to which Ld . | i 15 . the products are applied, the presence of free ale ; cohol and salt in the cured composition is consie dered to be disadvantageous in other applications for which ester-cured phenolics might be considered, particularly where there is need for high electrical resistance and/or water resistance.

In an attempt to remedy at least part of this . -: deficiency, it was proposed in GB-A No. 2,140,017, to employ a formate or acetate ester of a monoe or a a ' polyhydric phenol reactive with formaldehyde as the . 25 ester curing agent for hardening alkaline phenolic oy, A , resole resins. In this case, the ester is obtained by esterifying the phenolic ~OH group(s) of the mono= or polyhydric phenol. On mixing this ester with alkaline phenolic resole resin, the ester is : saponified as a consequence of the action of the al« kali in the resin component. when the ester is sapo~ nified, the original phenol which formed the alcohol component of the ester is released and thereby made available for reacting into the resin structure. 0 Since the phenol is reactive with formaldehyde, it also serves to bind any formaldehyde which is uncom~ bined in the resin or is liberated subsequently. The salt of the acid component of the ester in this case remains as a non=resinous by-product in the cured compositions . It is further characteristic of ester cured . phenolic resole systems heretofore produced that they are effective only when a strong alkali is employed.

In most practical applications, only sodium or potas sium hydroxide produce satisfactory compositions. ’ | Phenolic resins produced with weaker bases either can- v not be set in a reasonable time using esters, or can be set only by additionally heating to high tempera- tures.

We have found that these and other disadvant~ lt

. } . ’ 26581 . > 3 . " ages can be avoided or, at least, substantially rew- } "+ duced by employing phenolic compounds containing ‘esterified methylol phenolic ring substituents, in’ ‘the presence of a base and a polar solvent in the preparation of a cured phenolic resin compositiony : }

By using these esterified phenolic compounds, the - release of alcohols during the saponification stage is avoided.

In a first aspect, the present invention pro« vides a method of making a cured phenolic resin come position which comprises reacting (1) an esterified phenolic compound containing . one or more phenolic hydroxyl groups and/or one or ~ more esterified phenolic hydréxyl groups and further : 15 containing one or more esterified methylol groups ~ | . positioned ortho and/or para to a phenolic hydroxyl group or esterified phenolic hydroxyl group, Co (2) an unesterified phenolic resole resin E © composition and oo (3) a base, in the presence of water and/or other polar solvent.

The esterified phenolic compound used in the present invention is a phenol or a phenol derivative oo containing one or more phenolic hydroxyl groups oo 25 and/or one or more esterified phenolic hydroxyl .

groups and further containing ome or more esterified methylol groups attached to a phenolic ring carbon atom at a position ortho and/or para to at least one ' phenolic hydroxyl group or to an esterified phenolic hydroxyl groupe Thus, it will be understood that the esterified phenolic compound used may be & MONO=, a di~ or a polyesterified methylolated mono=, di- or polynuclear phenol wherein at least one esteri- fied methylol group is attached to an aromatic ring carbon atom ortho or para to a phenolic hydroxyl group or esterified phenolic hydroxyl groups.

By the term “mononuclear phenol', we means a non-polymeric compound having an aromatic nucleus to which is directly attached at least one hydroxyl group. Examples of mononuclear phenols include, but are not restricted to, phenol itself, homologues of phenol such as o-y m= Or p-cresol, 3,5=~xylen=~1-0l, ’ t-butyl phenol, octyl phenol, n-nonyl phenol, and o- or p-phenylphencl and derivatives of phenol such as resorcinol, l,l4'=dihydroxydiphenyl ether and 4,4'= ! dihydroxydiphenyl thioether. By the terms “dinuclear -- phenol’ and "polynuclear phenol" we mean compounds formed by the condensation reaction of two or more molecules of a mononuclear phenol with one or more molecules of a phenolwreactive aldehyde or ketone,

Examples include, but are not limited to, resinous reaction products of phenol, homologues of phenol or derivatives thereof (for example, o-, m= Or p= cresol, 3,5-xylan-l-oly ethyl phenol, o- or p= | phenylphenol, resorcinol, phloroglucinol, pyrogallol, h,4'=dihydroxydiphenyl, k,4'=dihydroxygdiphenyl ether and (&,4'wdihydroxydiphenyl thio ether) with an al- ’ dehyde (such as formaldehyde, acetaldehyde, furfurale dehyde and benzaldehyde, and mixtures thereof) or with a ketone (such as acetone and cyclohexanone )e

Furthermore, mixtures of aldehyde-reactive phenols such as mixed cresol isomers, xylenols and phenolic B : "blends such as those obtained from coal tar fractiona- Le Co . tion and cashew nut shell liquid, can be employed as : oo - all or part of the phenol component. Lo Ce Cn oY “ : The above-mentioned dinuclear and polynuclear = oo oo / - methyld groups are especially useful in the present Lo | ; } invention in view of their own ability to form cured SA resin compositions when reacted with a base in the . presence of water and/or other polar solvent) Theres fore, according to a second aspect, the present in= vention provides the use, as a chemical precursor to ‘a cured phenolic resin composition, of an esteri-~ fied phenolic compound comprising an esterified mew thylol group-containing derivative of a di~ or poly= -? :

nuclear condensation product of a phenol and a phenol-reactive aldehyde or ketone, wherein the said derivative contains one or more phenolic hy- droxyl groups and/or one or more esterified phenolic hydroxyl groups and contains one or more esterified methylol groups positioned ortho and/or para to a phenolic hydroxyl group or esterified phenolic hye~ droxyl group, the said esterified phenolic compound forming a cured phenolic resin composition on re= action with a base in the presence of water and/or other polar solvent.

Such an esterified phenolic compound may be used in a method of making a cured phenolic resin composition which comprises reacting the esterified phenolic compound with a base, in the . presence of water and/or other polar solvent. : As mentioned above, the phenolic compounds which have use according to the present invention in the production of phenolic resin compositions contain one or more esterified methylol groups located ortho and/or para to a phenolic hydroxyl group or » esterified phenolic hydroxyl group.

By the term .. westerified methylol group" as used herein, we mean an organocarbonyl ;oxymethylene group or substituted derivative thereof.

By the term "methylol group" 25 . we mean a group of the general formula

.

R

( : =CwOH : -

K wherein R is H, an aliphatic or aromatic. hydrooars byl or an heterocyclic group. ; | i : Typically, the phenolic compounds having

Co 5 use in the various aspects and embodiments of the present invention may be prepared from an approe priate me thylol-containing phenol or phenol derivae Cy tive by reacting the same with an esterifying res J - oo . agent. The methylolecontaining phenol or phemol dew

Por eb me Sle eden de as bam ah pty nb Rd a de bE ese] ak ibm es ai rivative may be produced by reacting formaldehyde, Bh or or other aldehyde (such as acetaldehyde, butyralde= . . hyde and furfuraldehyde), with the apprepriate phenol : ‘ or derivative thereof. : Co } | ) For reasons of availability and reasonable cost, coupled with repeatability and freedom from strong or offensive odors, the preferred type of phenolic : compound is one based on a condensation product of . phenol and formaldehyde, Such condensation products . - may be manufactured in known ways by reacting pheaol and formaldehyde in the presence of acid or basic cata : lysts although the production of such products does ‘ not form part of this invention. Where basic cataw ~ i . lysts are employed for this purpose, the resultant - * phenol-formaldehyde condensation products (resole . Co 25 resins) will possess free methylol groups in a prow portion which will depend primarily upon the ratio of formaldehyde to phenol. These groups are attached to phenolic ring carbon atoms ortho and/or para to the phenolic hydroxyl groups. However, where acid catalysts are employed, the resultant phenol~formale- dehyde condensation products do not normally contain methylol groups. Such products may form suitable starting materials, however, if a methylolation step, using formaldehyde under neutral or alkaline condi tions, is carried out subsequent to the manufacture of the acid catalyzed condensation product and prior to esterification. . . Similarly, where the phenolic compound is a condensation reaction product of a phenol and a phenol=reactive ketone, methylolation will be neces- sary prior to esterification. Such methylolation ’ cen be readily carried out by reaction with formal- dehyde under neutral or alkaline conditions.

Of these various methods of preparing the , 20 methylol-containing phenol or phenol derivativey we . prefer to prepare & phenol-formaldehyde condensa ” tion product in the presence of a basic catalyst (i.e. a resole resin) since such avoids the need for a further methylolation step. In such a cone

Co 25 densation product, the mole ratio of phenol: formal 3 - 10 w=

: ~ . . i dehyde will typically be in the range of from | i } 1:1l.2 to 113.0, preferably from 111.5 to 133.0. ’ . | The amount of alkali used as condensation catalyst will typically be about 1-2% by weight based on the ° weight of the phenol, generally sufficient to maine tain a pH of at least 8, but may be considerably higher. The degree of condensation of such a resole B , resin can conveniently be described by reference to : two parameters; the residual solids on heating at ~ h X+ J 100°C. to constant weight and the viscosity of the | Co - resole solution. The resole resins most preferably - used as the methylol-containing phenolic derivatives CL ye. oo oo to ve esterified to produce the esterified phemolic ; Moan ~. compounds will have a solids content of tron 30 to, i 5 ELAR -

Co 15° 95%, preferably 50 to 85%, by weight and a visossity eal " a . of from 0.1 to 100 poises, preferably 1 to 25 voises, SUR

EE at 25°C. Typical examples of condensation catalyst = Co Sh \ } include the oxides and hydroxides of sodium, potas= .- ) Lo . sium, lithium, barium, calcium, magnesiun and anines > : oo bo and ammoniga 5 | . B Co .

Ce oo The me thylol~containing phenol or phencl-dskic J Lo

Co ‘on N : vative thus prepared may then be esterified td pros oo - duce the desired esterified phenolic compound containe - ) ing one or more esterified methylol groups positioned a 25 ortho and/or para to a phenolic hydroxyl group or . : “ll = esterified phenolic hydroxyl group. The esters of the methylol-containing phenols or phenol deriva- tives contemplated are organic carboxylate esters. these esters may be derivable from any aliphatic, alicyclic or aromatic mono- di~ or polybasic acid capable of forming esters with methylol groups. It is also possible for an esterified methylol-containing phenolic compound to contain ester groups derived from more than one of these acids. For most pure

RU) poses, however, the esters will be those formed from lower carboxylic acids, especially formic acid and acetic acid. Where reference herein is made to the acid component of the ester group, this is intended only as descriptive of the type of group and it is not intended to indicate that the acid itself need be employed for the manufacture of the methylol esters

In fact, the ester may be formed in any known way and the procedure adopted may be varied, as will be known . to those skilled in the art, to suit the particular compounds being produced. Examples of some methods * of esterification that may be used include: . on (1) reaction of a methylol compound with acid , anhydride, mixed anhydride or acid chloride, typical- ly in the presence of a suitable catalyst} s 25 (2) ester exchange between a methylol compound and a suitable carboxylic acid ester in the presence of a suitable catalyst or by acid interchange as dese : . eribed, for example, in U.S. pat. No. 2,544,365; and CL (3) treatment of a methylol compound with ketene, diketene or their derivatives, i It is also possible to produce the desired phenolic compounds by the action of an acid anhydride on mono=, di= or tri-dialkylaminomethyl substituted _ phenols or phenol derivatives. - 10 Thus in some cases a carboxylic acid anhydride : may be employed to esterify the phenolic compound with advantage, instead of the carboxylic acid. Ale : ternatively, the ester may be formed from the corres - ; - oo oo ‘ponding acid chloride. As mentioned above, i pre= : : 15 “ferred phenolic compound having use in the present | oo oo > Co | invention comprises a phenolic resin containing oo CL _

So esterified methylol groups. In such a case, it is . oo ' the methylol-containing phenolic resin that vill be Lo esterified. Generally speaking, however, phenolic - i. resole resins are acid sensitive and in most cases | 5 it will be necessary to esterify the methylel groups, . Co and optionally the phenolic hydroxyl groups, en a = Co phenolic resin by an indirect route, so as te avoid a : gelation of the resin. The tendency to gel may be i . ‘reduced or eliminated by blocking the phenolic «OH * oo

EE co DN ae Tn LR

SE RE

. . . : . V0 ’ : } y Lt ~ : ; Jf Co group by esterifying or etherifying it, as described, for example, in DE~C Noe 471,561. Obviously, any catalyst employed to promote the esterification re- action must not be capable of entering into further reaction with the esterified methylol groups of the product of the esterification reaction under the ree action conditions used. An example of a suitable esterification catalyst is pyridine.

A preferred procedure is to form the acetate ester of methylol-containing phenolic compounds by introducing ketene into a solution of the methyble containing phenolic compound. In this case, the . ketene is preferably generated immediately prior to use, typically in equipment such as that described in U.S. Pate No. 2,541,471 or U.S. Pato Noe 34259,469.

By reacting the phenolic compound with diketene in a gimilar way, the acetoacetate ester of the phenolic compound is obtained. Other esters may be formed by ester exchange.

Suitable ester groups include, but are not * restricted to formate, acetate, acetoacetate, acryl= ‘a ate, propionate, lactate, crotonate, methacrylate, butyrate, isobutyrate, caproate, cpprylate, benzoate, toluate, p-~amino~benzoate, p~hydroxybenzoate, sali~ : 25 cylate, cinnamate, laurrate, myristate, palmitate, - 1h = eleate, ricinoleate, stearate, oxalate, succinate, fumarate, maleate, adipate, phthalate, azelate and sebacate. Acetate esters form a particularly pres : ferred class of compounds according to the present invention. ’

One particular class of methylol esters which is particularly useful is that of the methylel hydroxybenzoates since, on saponification of the ester in the presence of a base, the hydroxybenzoate lo moiety is, by virtue of its phenolic hydroxyl .gr oup, - capable of linking inte the phenolic resin stiucture Th wh and, by virtue of its carboxylate group, capable or 3 B ni en Bg onng any baste BdtEL Lon" Eh FILS Chapman her ic

Co linked molecule. Thus, on the saponification of oo Co hydroxybenzoate esters of methylolwcontaining phenew oo - “ : lic compounds, in the presence of a base, there is no release either of an alcohol component er of a salt unlike the case with prior art ester curing systems for alkaline phenolic resins. Another class having similar capabilities to hydroxybenzoates comprises Co the hydroxyphenylalkylcarboxylates which will have the same effect as hjdroxybenzoates although hydroxye : phenylalkyl carboxylic acids may form esters more ) . . easily with methylolated phenolic resins. ‘

These hydroxybenzoate and hydroxyphenylalkyl . / “15 N IRE carboxylate esters form yet a further aspect of the present invention.

Accordingly, the present inven=- tion provides a phenolic compound having one or more phenolic hydroxyl groups and/or one or more esterified phenolic hydroxyl groups and, at phenolic ring positions ortho and/or para to a phenolic hye droxyl group or esterified phenolic hydroxyl group, one or more groups of the general formula (1) (1) 0 on, —ohten —}( OQ (oH), —- z wherein R is a saturated linear or branched lower hydrocarbyl group, x=0 or 1, y = 1 to 3 and z = 1 or 2, such that when x = Oy 2 = 1. A preferred class of phenolic compounds according to this aspect of ’ the invention comprises resinous phenol=formaldehyde ” 15 condensation products containing two or more substi=~ tuent groups of the general formula I above at posi ‘ tions ortho and/or para to phenolic hydroxyl groups or esterified phenolic hydroxyl groups in the mole= cule, Examples of the hydroxybenzoate and hydroxy= phenylalkyl carboxylate esters include those derie : ~ vable from the acids 3,5~dihydroxybenzoic acid, i= hydroxyphenylacetic acid, 244 ,6~trihydroxybenzoic acid, b-hydroxybenzoic acid, b,bebis(4=hydroxyphenyl)e valeric acid, gallic acid and salicylic acid.

The list of suitable ester groups mentioned above includes some ester groups derived from acids i which are themselves capable of undergoing polymeri- zation (e.g. acrylate and methacrylate). It is, - oo © accordingly, posiéible to use a phenolic compound, as precurser te a cured phenolic resin, which contains ‘methylol esters of such acids. On saponificatien in x } | . the presence of the base, a polymerizable salt is ree ’ leased which can then be made to polymerize to form . mo a high molecular weight materiel, ’ Because phenol=formaldehyde rescles are se unstable and tend to form higher molecular weight - | : materials by condensation polymerization even at am- bient temperatures, conditions for esterification are oo very critical Therefore, as will be understoed from the above, the rdaction conditions conventionally ’ ’ employed in the preparation of esters from carboxylic acids and stable alcohols, such as methyl and ethyl eo 25 alcohols, will not always be suitable in the esterie vo | el? = oo oo ER fication of the methylol groups attached to aromae tic nuclei in phenol~formaldehyde resole resins.

Furthermore, the presence of a carboxylic acid may, itself, cause polymerization of low molecular weight phenol alcohols present in a resole composition.

Thus it is preferred to add the acid slowly to the resole, so that only mildly acid conditions prevail during the esterification reaction.

Solvents, such as, ethers or ketones, may conveniently be used, particularly in the case of higher molecular weight resoles, to dissolve the res sole and facilitate uniform reaction.

Since the esterification reaction evolves water, it may be accelerated by the use of none aqueous conditions, as well as by the use of a low= boiling solvent capable of forming an azeotrope with water.

The esters of the present invention are pres ferably prepared by choosing conditions which pres ferentially esterify the ~CH, 0H group and not the » phenolic ~OH groupe However, as it is clear from the above, it is within the scope of the various aspects and embodiments of the present invention to use esteri~ fied methylol-containing phenolic derivatives wherein some or even all of the phenolic hydroxyl groups thems w 18 = pelves are esterified. The latter will generally be slower to react but will also exhibit greater storage stability because of the inactivation of the phenolic -OH group.

Generally, when an acid is used to esterify the phenolic compound, the preferred amount of acid used will be equal, on a molar basis, to the content of free methylol groups. However, in cases where a plurality of methylol groups is present, it is pos=- sible to esterify only a preportion of the methylol groups, so that the remaining unesterified methylel . groups allow the product to be thermally polymerized at a later stage. This could, for example, be a con= : venient means of retaining a degree of thermoplastie city in the producte oo ~ On the other hand, an excess of acid may be no required to induce esterification at Rew temperature )

Ideally, any residual free acid should be removed ‘ from esterified methylol-containing phenolic come Co pound before the latter is reacted with a base in the oo presence of water or other polar solvent to produce oo a phenolic resin composition since any residual free . acid present in the esterified phenolic compound will i : compete with the esterified phenolic compound fer Co reaction with the base. | Co oe Co : “19 = oi,

As mentioned above, the esterified phenolic com- pounds react with a base in the presence of water or other polar solvent. =Ixsmples of polar solvents that cen be used in the present invention instend of water include methonol, ethanol, industrial methylated spirits (1148), formmmide, N,N-dimethylformemide, dimethylacet- amide, triethanolamine end glycerol.

In the application of the present invention to the production of foundry cores nnd moulds, we have found that the strength of sand cores is improved if pert or all of the polar solvent used is a glycol, such as ethylene gly- col or diethylene glycol, an ether alcohol, such as me- thoxyethanol, ethoxyethenol, phenoxyethanol or ethyl digol (i.e. ethylether of diethylene glycol), or a ketoalcohol such as diacetone alcohol. Typical totrl solvent addi- tions are in the renge of from 1 to 507, preferably 1-307, by weight based on the total weight of the other components in the composition. The use of a non-aqueous polar solvent will be desirsble in gpplications of the invention vhere the presence of weter could have n deleterious effect on the properties of the final product.

The base used in the »resent invention may be any material or mixture of materials, yhich, vhen added in a suitable omount to the composition comprising on esteri-~ fied phenolic compound containing one or more esterified

BAD ORIGINAL eT methylol groups, renders the composition alkaline which, ‘to in the case of agueous systems, means that the base is one that is capable of raising the pH of the composition to a value above 7. The amount of base required to ’ achieve this desired 21kalinity in the composition lerge- ly depends on the identify of the base used and on vhether the composition to which the base is edded contains any : chemical species vhich are reactive towards the bases

For instonce, if the esterified phenolic compound contains any base-reactive chemlcal groups and/or if the composition containing the esterified phenolic compounds additionally contains any base-reactive compounds which groups or compounds would have the effect of neutraliz- ing the base vhen added, then obviously the base should ’ be used in en amount which is in excess of the amount ~ required to neutralize any such base-reactive chemical groups and/or such base-reactive compounds present’ Most inorganic bases and many organic emines are suitable for reacting with the esterified phenolic compounds s The ease with which they saponify the resole esters deter- mines the rate of gelation and the minimum temperature at which gelation occurss .

The base, used to saponify the esterified methyl- . ol-¢ontaining phenolic compound to form a phenolic resin composition according to the invention mey take the form / : - 21 - Co -

BAD CH

. i re ‘ .. ’ - i Ea sha !

of a gos, a low boiling poirt liquid or the vapor there~ of, a2 liquid material or a solution of sm rllkeli or a solid. Suitable materisls include: (i) oxides 2nd hy- droxides of nlkeli and elkaline enrth metals, for exrm-— ple, sodium, potassium, lithium, barium, calcium end meg- nesium; (ii) oxides end hydroxides of other metols vihi ch exhibit nlkeline or amphoteric properties, such es zinc oxide; (iit) ammonia, quoternary smmonium, hydroxides, ali- phatic elicyelic or nromatic secondary and tertiary amines ond Mannich bases, for exemple, dimethylomine, trimethyl—~ emine, triethylamine, 0, T-dimethylethylemine, diethylene- triemine, triethylenetetroamine, 2, 4-bis (dimethy Lemino~ methyl )phenol nnd 2, 4, 6=tris (dimethylaminonethyl Jphenol. #11 bases tend to screlerate the rate of heat gela- tion of phenol-formaldehyde resoles but the effect is more pronounced with the esterified resins. Because of the modern emphasis on energy saving, nccelerntion of heat curing and cnusing gelation at room temperature ares im=- - portant properties of the materials of the present inven- tion.

The rate of reaction between the base and the esterified methylol containing phenolic compound is affected, inter by the solubility ond by the functionality * of the base nnd, where the base is an inorganic alkaline material, by the position of the cation in the electro-

BAD ORIGINAL a mae

' ! . : | : | : . ' chemical series. According to our findings, in general the rate of reaction between the base and the esteri-. fied methylol containing phenolic compound when the base i8 a secondary amine is lower than when the base i8 a tertiary amine, which in turn is lower than when the base is = alkali or alkaline earth metal oxlde or © hydroxide. We have found that alkali and alkaline earth metal oxides and hydroxides can cause extremely rapid curing of same esterified methylol containing phenolic ~ resole resins at embient temperature. There ere, how~ - ". ever, some applications where it mey be useful or desir- : able to have the esterified methylol containing phenolic compound undergo cure only slowly, perhaps only at ele- To vated temperatures, and in such applications the slover :

S15 reacting secondary and tertiary amines may be used’ . ~ There is, a particular application where the use : of a Mannich base as the basic material in the present invention gives certain advantages. This is in the pro- } duction of cured phenolic resins vhich have a reduced con- i tact of inorganic ions, especielly metal cations, and

TL } which therefore are more ‘electrically insulating. Fur- " thermore, we have found that the presence of water or : other poler solvent is not required for the reaction to : - proceed in the case where the base used is a Mannich base. : 25 Accordingly, the present invention in a further aspect oo / -235- _

BAD ORIGINAL

. ' ala age. Co provides a method of making a cured phenolic resin hav- ing reduced inorganic ion content which comprises react- ing (1) an esterified phenolic compound comprising en esterified methylol group=~containing derivative of a con- densation reaction product obtained by reacting two or more molecules of a monomiclesr phenol =nd one or more molecules of a phenol-reactive aldehyde or ketone, which derivative contains one or more phenolic hydroxyl groups and/or one or more esterified phenolic hydroxyl groups and containing one or more esterified methylol groups positioned ortho snd/or pers to a phenolic hydroxyl group or esterified phenolic hydroxyl group, and (2) a Monnich base. Treferably, the Mannich base is 2,4,6-tris (dimethyleminonethyl)phenols

We have found that vhen a basic alkaline earth metal compound, especially an oxide or hydroxide of magnesium or calcium, is used (in the presence of water or other = polar solvent) to saponify the esterified phenolic com- pound, a gelled phenolic resin havine good gel strength is produced. Thus, in a preferred embodiment, the base : used in the present invention vill be an oxide or hydroxide of magnesium cr calcium, Although we do not vish to be held to any particular theory, it is considered that the high gel strengths obtained by the use of a basic alkaline

BAD ORIGINAL

J \ . . . \ . . . 3 earth compound result, at least partly, from en elec~ : tronic "bridging" interaction between the bivalent : , alkaline earth metal ion and the hydroxyl groups of the. : * phenolic materials. hig appears to induce extra coupl- ing between the phenolic resin molecules thereby affect- ing a harder gel. This effect is surprisingly not res- tricted to esterified phenolic compounds comprising di- or polymiclear phenols containing a plurd ity of esteri-

Co fied methylol groups but is also seen when the esterified, phenolic compound is a monomclear phenol, as described . earlier, which contains one or more esterified methy lol groups. Thus, in a further aspect, the present invention : provides a method of making a phenolic resin composition ‘ comprising reacting a phenolic compound comprising an oo . 15 esterified monomeclear phenol containing one or more a“ phenolic hydroxyl groups and/or one or more esterified : ’ ; phenolic hydroxyl groups and further containing one or more esterified methylol groups attached to the aromatic } ring at a position ortho and/or para to a phenolic hy- . . 20 droxyl group or esterified phenolic hydroxyl group with a basic alkaline earth metal compound in the presence of : ’ water and/or other polar sblvent, The present invention , also provides the use, as a chemical precursor to a gelled BE phenolic resin, of an esterified monomiclear phenol con- taining one or more phenolic hydroxyl groups and/or one / ’ . -25 - | ol

Ca BAD ORIGINAL . | Tea ’

or more esterified hydroxyl groups and further contain- ‘ ing one or more esterified methylol groups attached to the aromatic ring at a position ortho end/or paras to a phenolic hydroxyl group or esterified phenolic hydroxyl group, the said esterified monomiclear phenol forming a gelled phenolic resin on reaction with a basic slkaline earth campound in the presence of water and/or other polar solvent.

Hormally, the base will be employed in an amount which is chemicnlly (stoichiometrieally) equivalent to the ester group content of the phenolic compound (4 10%). ; However, for some applications it might be necesssry or de- sirable to keep free ester present and for others, an ex-~ cess of base may be present, In the case where the base used in the present invention is an alkali metal com- pound, the molar ratio of total phenol; total alkali metal : in the sgy composition will typically be within the range of from 1:0.3 to 1:1.4. The use of any higher ratio may result in too fast a reaction while ratios lower then 0.3 mole of alkali per mole of phenol mgy leave unreacted ester and, therefore, give lower fingl strengths. Preferably, the polar ratio of total phenol: total alkali in the com- position will be in the range of from 1:0,5 to 1:1.1.

Prom the above, it will be understood that relative- ly mild bases, e.g. calcium or magnesium hydroxide, can - 26 =

ARAL BAD ORIGINAL

- : \ : be used to saponify the esterified methylol-containing phenolic resins which, upon saponification at room tem- perature, form cured phenolic resin compositions, As mentioned previously, such relatively weak bases do not glve satisfactory compositions at room temperature when used in the prior art ester curing of alkaline phenolic resins. Since these relatively mild bases form salts with the acid component of an ester released on saponi- fication of the esterified methylol-containing phenolic ’ compound which salte are less soluble then the correspond- ing sodium or potassium salts, the use of relatively mild bases in the present invention makes it possible to form phenolic resin compositiorshaving reduced water estract- ability.

In the first aspect of the invention described > earlier, the esterified phenolic compound is reacted with an unesterified phenolic rescle resin composition end a ) base in the presence of water and/or other poler solvent. : ~The esterified phenolic compound will be used in the per=- formance of this first aspect of the present invention in an amount typically from 10-120% by weight based on the weight of the unesterified phenolic resole resin

Preferably, the emount of esterified phenolic compound used will be from 30-80% by weight of the unesterified : 25 phenolic resole resin. }

Sib * -27 = ]

BAD ORIGINAL

So anti

Resole resins are produced by the reaction of a phenol and a moler excess of a phenol-reactive aldehyde typically in the presence of an alkali or slknline earth metal compound as catalyst. Methods of moking phenolic resole resins srewell known end do not need to be described in detail here, Typically, the recole resin will be a phenol-formaldelyde resin produced by reacting phenol and formaldehyde in a molar ratio (phenol: formaldehyde) within the range of from 1:1 to 1:3. The unesterified phenolic resole resin will usually be used in solution, especially os on agueous solution of the alkali metal galt of the phenol-formaldehyde resole resin.

Le According to the various aspects, end embodiments ) of the invention, other additives may also be incorporated . 15 with the esterified phenolic compound, the basic material ; and/or with the aqueous or polar solvent. Particularly useful are solutions of materials vhich could co-react with the esterified methylol-containing phenolic com- pounds or with the phenolic meterizls resulting from the © 20 saponification of the esters, In addition to the aqueous " solutions of alknli metal solts of phenolic resole resins - already mentioned, one might adventageously incorporate with the other components a volymeric materirl such as polyvinyl alcohol, cellulose and casein. Furthermore, . 25 a silane, such as grmmaaminopropyl triethoxy silome, mey ’ Apel - 28 - BAD ORIGINAL also be incorporated to promote adhesion, particularly in applications such as the production of foundry moulds and cores where the phenolic resin is used as a binder for a gramlar refractory material.

In yet'a further embodiment of the invention, an unesterified phenolic resole may be combined with elksli end water ond mixed with an esterified methylol-contain- ing phenolic, resin at the time of use. Such a procedure cen result in almost instentaneous gelation, even at room + temperature, Consequently, this procedure may conve~ niently be employed in processes such as the so-called ) G " separate application process" for bonding surfaces. In }

CTT hte process, a fizst component of o system comprising CT two mutually resictive ingredient, is applied in a thin film to one of the surfaces to be bonded, while the second ) : ~ component is applied to the mating face. Bonding is effected by bringing the two surfaces quickly together . under pressure, This process has the advantage thet working life constraints are overcome vhile retaining short setting times at low temperatures. In the above embodiment in accordance with the invention, the second component is conveniently an aqueous, alkaline solution of a phenol-formaldehyde resole resin, preferably in the : form of a solution in ggueous potmssium or sodium hy- droxide. - 29 ~

BAD ORIGINAL

HA .

As is vell~knovn in the phenolic resin art, in some applications rapid cure of a phenolic resin may be a disadvantage ond steps ave taken to slow down and con- trol the rate of curing of the phenolic resin. For example, in the production of foundry moulds and cores from a foundry sand composition containing so resin binder and a curing agent for the resin, the sand composition must have a sufficiently long bench life, i.e. it must remain workable for a sufficiently long time to enable the moulds or cores to be msde. It may, however, be the case that an esterified methylol containing phenolic re- sole resin cures too rapidly in the presence of a base and water or other polesr solvent to be workable for a sufficiently long time for some such rpplications. This problem can be overcome by ueing a combination of an esterified nethylol containing phenolic resole resin and a conventional ester curing srent to cure an unesterified rhenol-formaldehyde resole resin under alknline condi- tions. It seems that the rate of curing of the unesteri- fied resole resin by the phenolic ester may be slowed dovn » and, therefore, controlled by the simultsneous use of con- ' : ventional ester curing sgents, such as diamcetin, triacetin, ) ethylene glycol diacetate, propylene glycol dincetate, butylene glycol acetate, organic carbonates (Cuftey propy- lene carbonate) nnd Lectones (e.g. propiolmctone, huty- a - 30 - :

Co AD ORIGINAL rolactone, valerolactone end caprolactone ). In order to * ensure homogeneity in the reaction mixture, the esteri- - fied methylol containing phenolic resin would be added to the mixture as a solution in the conventional ester 5 during agent. ; In eddition to the remarkable speed of reaction that may be achieved using the esterified methylol con- taining phenolic resins and their ability to undergo gela- tion at room temperature in the presence of weaker bases than those required by the phenolic resoles cured with . separate esters of the prior art, the campositions in accordance with the invention have a mmber of other pro- . perties which clearly digtinguish them over the composi- tions mown hitherto.

The known products produced by employing a sepa=- - » rate ester to cure alkaline phenolic resoles are in- . } variably of a dark red color. Using the process of the a invention, almost colorless or white or light colored products may be produced. This is of significence in : ) 20 certain applications of the present invention vhere the ’ oo products ere required to have an aesthetic appeal, for - instance in many surface coating applications, decora- tive castings, adhesives for laminates and adhesive applications where there is a possibility of "billed- : through" to a visible surface, While acid phenolic re— -31 - :

Co Tg | BAD ORIGINAL, im Co sins of light color have previously been produced, vith the limitations that this introduces, we believe that this property has not previously been obtained with al-~ kaline phenolic resins.

The esters of methylolated phenolic resins are generally insoluble in water. We have found, however, that the curing reaction with bascs does not take place or takes place less rapidly or less completely in the ab- sence of water or ether poler solvent which is necessary for the initial saponification step. Thus, according to another embodiment, the invention provides a composi- tion comprising an esterified methylol-containing phenolic regin, in an essentially anhydrous condition, and an essen— tially anhydrous base, such as calcium oxide or magnesium oxide, which composition is capable of forming a cured phenolic resin composition when contacted with water. A rapid reaction may be initieted by contacting the anhy- drous mixture with water. This contact with water can be brought abot by the use of noist air or steam, It will be understood, therefore, thnt this forms the basis of a p gas or vapor-curing technique for the cure of phenolic . resin compositions. This embodiment has a practical application in the production of moisture-curable surface coatings.

A further application of the present invention -32 -

Cay o BAD ORIGINAL

. which maltes use of the ability of a composition compris- ’ ing a mixture of an esterified methylol containing phe- : nolic resin in an anhydrous condition amd en anhydrous - base to form a cured phenolic resin when contacted with ’ water vapor or steam is in the production of foundry moulds and cores, Thus, according to yet a further em=- bodiment the present invention provides a method of mgk- ing a foundry mould or core vhich comprises mixing a gramlar refractory material containing substantially Te no moisture with an amount effective to bind said gramlar refractory material of an anhydrous esterified methylol containing phenolic resin and with an amount effective to saponify said esterified methylol containing phenolic re=- gin of an anhydrous base, forming the mixture into the : 15 desired shape ond then passing water vapor and/or stemm » through the shaped mixture whereby the base and the esterified methylol containing phenolic resin react to- } gether in the presence of moisture to form a cured phenolic resin which binds the granular refractory material. In this embodiment, the granular refractory material is ty- pleally a foundry sand which is substantially dehydrated prior to being mixed with the other components. Many types of sand conventionally used in the production of . foundry moulds and cores are themselves basic and if such } 25 alkaline sands are used in the embodiment of the present .

Coe 3 - BAD ORIGINAL:

invention described above, r seporcte addition of mn anhydrous base may be omitted from the mixture used to make the foundry mould or core, As stated above, in order to bring about the cure of the phenolic resin, the mixture is gassed with water vrpor and/or steam.

Gnssing will tyoienlly be nchieved by sucking stem and/or water vapor obtained from a steom generator through the shaped mixture of send, esterified resin snd base in a core box, Titted with perforated plates, by meens of a vacuum applied at one of the perforated plates. Unlike other gas curing techniques used in the production of foundry moulds and cores, the embodiment of the present invention described above avoids the use of noxious, flammable and relatively expensive gassing catalysts to effect the cure of the phenolic resin binderd

The compositions of the invention, es described above, have many various applicetione including contings, castings, binders for foundry use, refractory binders and adhesives for wood and metol components. Furthermore, compositions can be fommed according to techniques knowm in the art.

In the cose of foundry mould or core mrmufacture, a major amount of a gramular refractory material, such as sand, may be mixed with a minor amount of an unesterified phenolic resole resin and an esterified phenolic compound / - 34 - penn HE BAD ORIGINAL as herein described in the presence of a base and water and/or other polar solvent whereby the unesterified ’ phenolic resole resin and the esterified phenolic com- . pound react to produce a cured phenolic resin composi- : 5 tion which binds the gramlar refractory material. Ty- pically, though not essentially, the amount of unesteri- fied phenolic resole resin used will be in the range of from 0,1 to 10% by weight based on the weight of the granular refractory meterial end the amount of esteri- fied phenolic compound used will be in the rangecsf from © 10 to 120% by weight based on the weight of the plenolie resole resin. Where the esterified phenolic compound is an esterified methylol group-containing derivative of a : di or polymiclear condensation product of a phenol and a . 15 phenol-reactive aldehyde or ketone, it is possible to ~ meke foundry moulds or cores sccording to the above with~- out the need for an unesterified phenolic resole resin

In such a case, the amount of esterified phenolic compound used will, in general though not essentially, be in the range of from 0,1 to 10% by weight based on the weight of the gramilar refractory material. It will be appre- : ciated that the actual amount of phenolie resin (whether unesterified or containing esterified methylol groups) required for addition to the gremler refractory material will depend on a mmber of factors including the molecular 1

Matra KE - 35 = 840 ORIGINAL weight of the resin, the nature of the esterified phenolie compound and the type and smount of base,

For use in illustrating the invention, the follow- ing esters were prepared:

Products A to BE are phenol-formaldehyde compounds and resins containing methylol groups.

Products I to XI are examples of esters mamfac- tured from the methylolated compounds using various re- agents and procedures.

Fxamples 1 to 12 and Application Examples 1 to 8 i1lustrate the invention and exemplify the polymerization of the phenolic esters in the presence of alkaline mate rials,

PREPARATION OF THE JETHYLOLATED PROUCTS

35 FOR ESTERIFICATION : PRODUCT A - SALIGENIN

Saligenin (orthomethylol phenol, 2-(hydroxymethyl) phenol)

This product was used as purchased from Aldrich

Chemical Comparny

PLROWCT B — PHENOL-FORLAIDEHYDE RESOLE ) (MOLAR RATIO F:P = 1,6:1; SOLIDS m= 70)

Phenol (1 mol) and 507 formalin {0.6 mol) were charged to a reaction vessel and the temperature maintained . - 36 = apne he BAD ORIGINAL below 40° C. whilst sodium hydroxide (0.004 mol) was added, The temperature was then roised to 80° C. The temperature was maintained at 80°C. while a second charge of 500% formalin (1.0 mol) was added slowly over * 30 minutes and the temperature maintained at 80° C. for a further 15 mimutes. The mixture was then held at 70°C. for a further 30 mimites, The pH was adjusted with p- toluene sulphonic acid solution 40 4.0 4/-0.2 and the volatiles distilled off under vacuum at 70°C. to a vis- cosity of 80 centistokes at 25°C. The resin was cooled to 60°C., the pH adjusted to 6.2 4/-0,02 with sodium hy~ : droxide, 0.027 moles of urea were added and the product further concentrated to a final viscosity of 500 cP at 25°C., cooled and discharged. !

Co. 15 PRODUCT C —. PHENOL-FORMAIDEHYDE RESOLE (MOLAR . | | RATIO F3P = 2.5:1; SOLIDS m 77%

Phenol (1 mol) and 50% formaldehyde (036 mol) were charged to a reaction vessel and the temperature held be- low 40%, vhile magnesium oxide (0.03 mol) was added and . Co 20 well dispersed. The temperature was then allowed to rise - to 70°C. over 30 mimites and maintained at this temperature while a second charge of 607 formaldehyde (1.9 mol) was added slowly over one hour snd then held for a further mimites, The temperature was then lowered to 55° cd /

Ci oT BAD ORIGINAL and vacuum distillation commenced until a viscosity of 85 e5t at 25°, wos obtained, the temperature wes then reised once more to 80°C. and held for one hour, the re- sin was then cooled to 65°C. md held rmtil the wnter dilutability reached 1:4 at 25%¢, The product was then cooled to room tempersture md dischnrged.

ERODUCT D_- MIENOL-FORALDRIYIE WSIS (MOLAR RATIO

F.p = 2.0:1; SOLIDS = 657

Phenol (1 mol) and 50" formaldehyde solution (0.6 mol) were charged into o recction vessel and the tem~ perature held ot 44°C, vhile 500, sodium hydroxide (0.04 mol) wes added, The mixture wns then heated to 80° C. and a second charge of 507 formsldehyde solution (1.4 mol) . wes Adnd slowly over a period of 25 minutes. The mix was then held at 80°C. until the viscosity reached 550 cP (nbout 6 hours). The product vrs finally cooled to room temperature and discharged.

IRODUCT E_IIENOL-FORVALDEIYDE RESOLE (MOTAR RATIO P:p = 1,8]:1; SOLIDS mw 60,57

A reactor was charged with 1,061.9 g (11.30 moles) ’ of phenol nnd 95.55g (0,768 moles) of a 45% aqueous so0-~ ~ ' lution of potassium hydroxide. This mixture was heated to 60°C., then 1,225.7 g (20.43 moles) of warm, 50 sgueos formaldehyde was added over 30 mimutes, vhile the : 25 temperature of the resction mixture rose to 105°¢, The 2 em BAD ORIGINAL

© reaction mixture was then cooled and held eat 75°C, ~ : 80°C. until a Gardner viscosity (25° CG.) of TU (approxi- mately 600 centistokes) was attained,

The resin solution was then rapidly cooled to room temperature. The yield of resin solution was 2263 ge The water content as determined by Kerl Fisher titra- tion was 32.1%. The free phenol content was 2.3%. The ) solids content, as determined by oven drying et 135°C, was 60.5%. The product was a resole made fram a reaction mixture having a F:P molar ratio of 1.81:1 and a potassium: phenol (K:P) molar ratio of 0.068:1l. Co

ESTERIFICATION CF THE METHYIOLATED PHENOLIC

H Tee vo iw tes SN © QOMPOUNDS © avin oT obit dmbadumiin ef am bp .

PRODUCT J - SALIGENIN MONOACETATE : 15 Acetic anhydride (59 ge. 0.58 mol) wes mixed with ’ pyridine (50 g) and Product A (72 go 0.58 mol) added slow- ly with stirring and cooling to prevent the temperature exceeding 50°C. The mixture was allowed to stand over- night st room temperature and then poured into a large excess of cold water. Diethyl ether was added and the : reaction product extracted then washed with water, 1% hy- @ drochloric acid and gain with waters

The orgenic layer was dried and the ether removed under vacuum leaving a pale yellow oil. / . -z - . ’

Ce 39 BAD ORIGINAL

PRODUCT II ~ SALIGENIN METHACRYLATE

Product A (13.5 fey 0.11 mol) was dissolved in py- ridine (8.6 zg) and dichloromethane (200 ml). HMetheacrylol chloride (11.4 0,11 mol.) in dichloromethane (50 mol) wes added slowly with stirring, vhilst the temperature was maintained below 40°C, The mixture stood for a further hour and was then refluxed for 20 mimutes, The product was cooled, washed with water, dilute acid and water again, i . dried over anhydrous sodium sulphate and evaporated under - vacuum to remove the solvent, ’ PRODUCT III - FORMULATED PRODUCT B

Formic acid (46 g) and acetic anhydride {102 g) were slowly mixed while the temperature was held below 45° 0. The mixture was left to stand for one hour at 45%¢, and then cautiously added to a mixture of Product

B (100 g) plus pyridine (7.9 g) vhile immersed in m ice/ water bath to hold the temper-ture below 20%. The mixture was then pllowed to stend overnight nt room temperature.

Ethyl acetate was then added to the mixture, which was washed several times with water, then with dilute acid ond finelly t vith water again, the organic phase was dried, filtered and . evaporated to dryness A viscous, straw-colored liquid (Pro- duct B formete) was obtained. . - 40 - .

Voi : BAD ORIGINA-

FRODUCT IVy — PARTLY ACETYLATED PRODUCT C

Product ¢ (50 g) and pyridine (75 g) were mixed end acetic snhydride (25 g) added cemtiously with stirr- : ing, the temperature being maintained below 40°C. The mixture was left overnight and then poured into a large excess of iced water. Ethyl acetate was added and the oo product extracted, washed with water several times, di- lute acid and finally water again, The organic leyer was dried and the solvent removed under vacuum,

FRODUCT IVh - HIGHLY ACETYLATED PRODUCT D

The procedure described for the preparation of

Product IVa was repeated but using Product ¢ (50 g), pyri- dine (75 g) and acetic anhydride (50 g)i : PRODUCT IVo - ACETYLATED PRODUCT C (USING KETENE)

RB 15 Product C (phenol-formaldehyde resole of F:P molar ratio 2,5:1) (400 g) was dissolved in acetone (100 ml) and stirred continously while ketene, generated in situ with a ketmne lamp, was passed for 6 hours at 0,5 mol per . - hour, The product was extracted into ethyl scetate, washed with water several times, then with dilute acid and finally with water again, The orgenic leyer was dried end the solvent removed under vacuum, A saponification value of 6.3 x 107 mol per grem was obtained. . i - / } | -H- BAD ORIGINAL

PRODUCT V ~ FORMULAIGD FROWUCT C

The procedure described for the nreporetion of

Product IIT was followed cxcept that Product C (200 g) wos used in plzee of Product BD.

IMOWCT VI ~ ACEIYLAED IRGDICT D (USING KITE)

Product D (90 g) wes dissolved in acetone (100 ml) and stirred contimiously while ketene (generated in situ using a ketene lamp) was passed for 2 hours at a rate of 0.5 mol per hour. The product wns extracted into ethyl cette, veshed with water several times, then weshed with dilute neid and the washed agein with water, The organic layer was then dried ond the solvent removed under

Vacuure

YRODUCT VII ~ SALIGENTI SATICYTLALE

Thionyl chloride (1 mol) in dichloromethane (400 ml) wee added dropwise and with constont stirring to a dis- persion of godium salicylate (1 mol) in dichloromethrne (800 ml). The mixture wns stirred for a further hour, then left to cool to room tempersture, cnre being taken ’ 20 to gvoid absorption of stmosrherie moisture. This solu- lution was then added dropwise -nd with vigorous stirring +0 a solution of Product A mol) and pyridine (2 mol) in dichloromethrne (1200 ml), After »ddition wns completed, the mixture was hested to 40°C, held nt this temperature ) 25 for 10 minutes and then pllowed to cool, The reaction

LT BAD ORIGINAL mixture was then washed several times vith water and

CL dilute acid until no traces of pyridine remained, The . organic phase was then dried over anhydrous sodium sul- phate, filtered and stripped of solvent to obtain sali- “ genin salicylate in 60% yield, )

FROWCT VIII ~ SALIGENIN DIACETATE : Acetic anhydride (82.3 g., 0.806 mol) was mixed - : with pyridine (130 g) and Product A (50 g, 0.403 mol) added slowly with stirring and cooling to prevent the temperature exceeding 50°C, The mixture was allowed to stand overnight at room temperature and then poured into a large excess of cold water. Diethyl ether was added and the reaction product extracted, washed with waters then washed with 1% hydrochloric acid and then again

BN 15 washed with water. The organic layer was dried and the ether removed under vacuum leaving an pale yellow oils

FRODUCT IX ~ DIACETAIT OF 2,6-DIMETHYIOL~ p=CRESOL gg compared to the theore- ticel possible gain of 2.5. g. The recovered methyl form- 20 . ate was returned to the flask, and the contents of the flask were permitted to stand for three days at embient (room) temperature. The volatiles were then stripped off until the flask weight remained constent: The yield of nonvolatile, wet solid product was 6.8 g. for a total - - gain of 1.8 g. Assuming that there were no side re- ‘BAD ORIGINAL ' ' 1 eed actions, this represented an approximately 707 conver- gion.

Upon treatment of a sample with 200 crustic in

NyH-dimethyl acetomide, the product ssmrle becsme hetero- genous and eventually separated into two layers. The up- per loyer wos light amber in color and was about tvice the volume of the lower layer. The lower leyer wns al- most colorless. The ‘top layer hed a consistency similar to that of medium panceke syrup.

EXJIPLES OF COMPOSITIONS IN ACCORDANCE

WITH THE INVENTION oo In the following exemples, vhere the Shore D gel hardness is quoted, this was measured using a Bareiss

Shore D hardness meter (Bareiss AG, 7938 Oberdisdingen,

Germany) as described in DIN 53 505(ISO Standard R 868).

An approximate gelation time was obtained by mixing 4.0 grams of the esterified phenolic with appropriate smounts of alkaline material and water (where used) and observing the time taken to form a gel. The observation was made unless otherwise stated, at an mmbient temperature of about : 20%. ’ SX AMFLE 7

About 10 g of rroduct IVa (acetylated Product C) was mixed with 5 ml of 45% potassium hydroxide solution.

This gave a gel time of 3%0 seconds nnd a hardness after

BAD ORIGINAL

—- Al -

26 hours at 20°C, of 45-50,

For the purposes of comparison, 10.0 g of Product

C containing 1.8 g of water was mixed with 3.2 ml of 70% aqueous potassium hydroxide solution and 3 g of triacetin, This gave a gel time approximately 24 hours end a hardness of less than 10 after 170 hours.

The faster gelation time ond increased hardness of the acetate ester of Product C over Product ¢ with . separate ester shows the advantage of the product in oo 10 accordance with the invention over the product in accor- dance with the invention over the product in accordance with the prior art.

EXAMPLE 2 : About 4.0 g of Product C acetate ester (Product

IVa) mixed with 1.04 of calcium oxide and 1 g water gave ~ a gel time of 30 seconds and a hardness of 75 after 170 hours at 20°C. oo By comparison, it was difficult to stir cateium ) oxide into a mixture of Product C and triacetin, since small lumps were produced. A non-hamogeneous product containing lumps of gel in liquid resin wes obtaineds

The present invention shows the advantage that al~- kaline earth metal alkalis may be used to produce useful products. Indeed the gelled material produced in this exemple shows a greater hardness than that shown in oo | = 45 = BAD ORIGINAL

«

Example I and this is thought to be due, in pert to some kind of electronic interaction between the bivnlent metal and the hydroxy proups in the phenolic compounds. This appears to induce exirs counling between the phenolic resin molecules thereby effacting a harder gel.

EXAMPLE 3 ibout 4 g of salipenin monoacetate (Product I) was ’ mixed vith 0.67 £ calcium oxide nnd 0.5 Fe viater added.

A gel time of GO seconds was obtained and a hardness aftor 144 hours of 34,

This model compound, because of the low F:P ratio and relatively low molecular weight would not be expected to form n gelled product through the renctions of the methylol groups plone. By nsing coleium oxide rs the alkaline curing naent a respectacle gel strength is ob- teined, egain illustrating the advantage of employing bi- valent metal ~lkelis.

About 4.0 £ of Product C acctote ester (Product ’ 20 IVa) mixed vith 0.77 £ of mornesiim oxide ~nd 1 pg water \ gave a gel time of 10-12 hours it hed a herdness of 65~ : 70 after 170 hours at 20°C.

The high hardness of the product ognin indicates a contribution from electronic interactions of the bi- . BAD ORIGINAL

; : valent metal and the hydroxy groups of the phenolic materiels., Exgmples 2 and 4 illustrate an important feature of the invention, which is the ability to adjust the reactivity of the system by employing different al- kalis as curing agents, whilst at the same time mointain- ing a product of useful hardness. .

EXMPLE 5

About 4 g of Product C formate ester (Product Vv) ~. mixed with 0.75 g calcium oxide and 0.5 g water gave a gel time of 1 mimte ond a hardness of 75-80 after 96 hours at 20°C. Lo

The diacetate of 2,6-dimethylol-p-cresol (DMPC) ry fini + ne bE me fy wes prepared by reacting 344 'g of’ #he dimethylol cresol mmm. of x whines odes Co

Co with 4.8 g of acetic anhydride in the presence of 7.8 g oo .

Lo 15 © of tetrahydrofuran, . After 66 hours at room temperature, the reaction ” . solution was diluted with 5.g of methylene dichloride, : ! then washed several times with 15 ml of cold water. An organic layer of about 10 g was ‘dried with 2 g of 10 en— hydrous sodium sulphates ’ ’

PARA CRESOL (DMPC) USING DIKETENE . A reaction vessel was charged vith 3.45 ge (0.02 : mols) of DMPC in 5 g of tetrahydrofuran and 0.1 g of en- . ; \ , - 47 =~ : BAD ORIGINAL hydrous sodium scetate., After these ingredients vere charged to the reactor, 3.4 g (0.4 moles) of diketene was added, This mixture was stirred vhile meintaining it at 25° = 35° C. by menns of a wober bath, Tor obout 4 hours. At the end of this time, the reaction mixture was essentially homogeneous. The resulting product vas the di(ncctoncetic) ester of DHPC,

PRODUCT XI ~ SALIGEWIH FORMATE

Snlipgenin formate was produced by the reaction of solipenin with methyl formate. Thus 5.0 g of saligenin and 20 g of methyl formate, together vith 0.1 g of imida~- zole, werc charged to a reactor flask that was equipved with a stirring bere. The mixture wos alloved to stand at anbient temperature for two days. 141d vacuum was then npplied to the reaction mix- ture ot room temperature, as the mixture was ngitasted using the stirring ber, to strip off volatiles. The yield of nonvolatile product was 6.3 ge.y a goin of 1.3 ge i Comparison with Exemple 2 shows that the acid func- tion of the ester may be varied without compromising the ' hordness of the gel produced.

About 4 g Product C acetate ester (Product IVe) was mixed with 1.9% g calcium oxide and varying amounts of i © © 25 . water. - 43 - GAD ORIGINAL : RS ot . Cor ;

WATER ADDED GEL TIME a 0.28 g 30 seconds 0.036 g 45 minutes

The present invention allows the regctivity of the sys- tem to be varied by the addition of water br other suit- : . able polar solvent.

EXAMPLE 7

About 4 g Product B formate ester (Product 111) mixed with 1.5 g 2,4,6-tris(dimethyl gninomethyl )phenol . 10 gave a gel time of 2-3 mimtes and a hardness of 60 after 72 hours.

In a different experiment, 4 g of Product III were . mixed with 1.5 ml of a 35% smmonia solution (squeous). - Te reaction mixture set in 1 mimite from 20°C. with mild exotherm to form a soft gels 4 g seligenin methacrylate (Product IT) mixed with 0.58 g calcium oxide followed by 0.5 g water gave a gel time of 1 mime and a herdness of 50-60 efter 24 hours. :

In a different experiment 4 g of Product III were : mixed with 1.5 mol of a 35% ammonia solution (aqueous): Bh

The reaction mixture set in 1 mimte from 20°C, with mild . , - 49 - : BAD ORIGINAL exotherm to form » soft gel.

About 4 g of Product C taken to different degrees of acetylation (Products IVa ond IVb) vhen mixed with 0.75 g calcium oxide snd 0,5 g water gave gel times of 30 seconds and 3 mimites respectively.

The degree of esterification may be used to very the properties of the system ns required.

EXAMPLE 10

Table I illustrates the improvement in resistence to extraction by water obtained from the gelled resin through the use of the compositions in accordance with the invention, es contrasted vith a prior art alkaline : phenol-fomaldehyde resin curcd in a typical manner with a conventional ester, :

In carrying out the tests, semples of the materials under test were gelled and allowed to cure for 10 days at 20%, after vhich they were ground and sieved to provide powders within the range 300 to 600 microns. The powders ’ 20 were then stirred into 100 ml of deionized water snd re- } fluxed for 3 hours. At the end of this time, the powdered material wos filtered off, weighed in a tored sintered glass filter crucible ond dried to constant weight at 100° 0. The sanples were then further extracted in a similar way but re- = 50 - BAD ORIGINAL

. plecing the water with acetone. . Resin 1 was KOH~-catalyzed phenol~formaldehyde re-

Co sole having an F:P molar ratio of 2,0:1, a K:P molar ratio of 0,745:1 and a solids content of 63.5% by weight. } 5 The first entry in the following table 1s for purposes of comparison only and employs triacetin (30 grams on 3 100 grams of resin) as curing esgent., The second entry ‘ shows the improvement brought about by employing the same : resin in accordance with the invention, using saligenin diacetate in plece of triacetin as the curing agents } . . + , / . -51 - :

CL BAD ORIGINAL

4 4 =

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Ss k H £9 E+ . ~ * o ° QO ~ ~~ 0 54 ne + — o Ny —~ ge Mm oo : , « f=] © . . 0 0 ® °c oc. eo 2 9 oN Qo oO ao AN a oN : ~~

Et [1] . o : av [4 VI] 0 ~~ lJ of ou Na

Bs Ra - 0 * ° EE +H o 8 = EK Ov O° n 1 2 oN RY no 4 0 % P-] 0 o E~] = wR F- +L = © od 0 0 * oO 0 Nn on . . =F 0 Nn faq © ao ~ © ® © wd ow & 42 1d al ad w 5B © » . od o ©

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Q + [a " O “dy n H of LL} 0 n @ o 0 Oo uo wu |] o a 0 2 3 QO " g 4 4 o 8 0 a 4 q £ I = 0 o f=] £4 = =o Gao <3 [= I HEH g > r

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Ba = 2 HO HH 8 3 8 9 [ne 33% 24d - [4] ° 0 eB mAag wnnunyv © w uw od > ©

Oo 8 a ~ ~Q ~O ~ o Wo 00 WAN 1 Oo a 0 — NS oN Su ~ ~~’ Sr = fn u i ° e 0 1m Eel ty Qo oH oO Hg

Oo 0 oO © oO © o fH of ort od m | oA 8 a 8 OA QL OP orl od ed + » 2 » ~ — ~4 LN] o

[3] js) ~~ ~ 0 ® oo 80 oo @ @ Or ~

B 0 oO Ww Ww oo O — Q 1 oO o QO — — ~ o a > = = [€] [al ld o 3 3 3 = a 7 G 9 o a $4 H $4 coe } . - 52 =

BAD ORIGINAL

Ce ;

EXAMPLE 131 Te

In this exemple, the diester, Produet IX, was evaluated as a crosslinker for sn alkeline phenolic re- sole. It proved’ to be very effective.

Thus, 3.4 g of the resin Product F. was mixed with 1.0 g water and 0.6 g 45% KOH solution, nnd cooled to room temperature and then quickly mixed with 1.0 g of

Product IX, This mixture become immobile in about 30 seconds, at ambient temperature.

EXAMPIE )2 in alkaline phenol-formaldehyde resin was made in : accordance with the teaching of U.S. Pat. No. 4,474,904,

This resin wes characterized by a fomaldehyde/phenol mole ratio of 1.8, a potassium/Phenol mole ratio of 0,63 . 15 and a solids content of 50% by weight.

About 0.6 g of the solution of 2,6+dimethylol-p- cresol diacetate obtained in Product IX having a concen- tration of about 50% was evaporated with an air stream to produce 0.3 g of an oily residue. Th this residue was added 1.2 g of the alkaline phenol-formaldehyde resin described above, The resin immediately gelleds '

EX/MPLES OF APPLICATIONS

Application Exemple 1-2-Port Surface Coating ) Agbout 4.0 g of Product C acetate ester (Product oo - 53 - BAD ORIGINAL oo

Ve) ving mixed with 0.77 a of mrgnesium oxide ~md 1 ml of water ond the mixture immediately painted onto wood and mild steel surfaces. The residual materinl did not gel for 10 hours at 20°¢, but the coating produced had reached n pencil hardness of 2B after 24 hours and HB after 1 week at 20%. ]

Application Example 2-= IMolsture-curing surface

Conting

About 4.0 g of Product C acetate ester (Product IVe), which was substantially dehydrated, were mived with 0.75 g of calcium oxide ~nd spread onto wood ond mild steel surfeces and allowed to stand in on etmosphere of high humidity at room temperature, Although the material in bulk was still liquid after 3 days, the costing had hardened to a glossy opaque finish after 10 hours at 20°

C. On the mild steel surfaca, the coating had reached a pencil hardness after 24 hours and after 1 veek at 20°¢., exceeded H,

Application Ixemple 3 ~ MNoisture-curing Foundry

Cores ’

About 15 g of the acetate ester of Product D (subs- $antinlly dehydrpted but containing 18 acetone) (Product

VI) wos mixed with 1 kg of Chelford 50 silica sand in a

Ridsdole laboratory core sand mixer for 30 mimutes. 4.5

Catala ede oT BAD ORIGINAL mim

, g of calcium oxide was added and mixed for 1 mimtel

The mix was rammed into an AFS green compression core box fitted with perforated plates.

A steam generator was employed with vacuum applied to the bottom plate to suck water vapor through the cores ‘

After passing steam for 30 seconds the core had hardened sufficiently to enable it to be stripped from the mould.

The core was hot to the touch, so that cure was also accelerated by heat. After standing for 2 hours at 20%, the core had a compression strength of 250 KN/m?.

Although it is recognized that the strength is poor . . by conventional standards, it serves to illustrate that the . :

Sov Ee pot "principle of water curing is a sound one," confirmed ~by mei Cpe we oo Example 6 and the surface coating of Example 2, The mix had stiffened and dried out after 30 mimites at 20°07, 80 that it was no longer useable, largely through the evapo- oo : | ration of the acetone, A core produced by this technique was immersed in cold water for 1 hour. Although softened slightly, it retained its shape, thus indicating that a significent degree of cure had been achieved. ~Anplication Example 4 = Refractory Bonding

The following semples of gelled material were submit- ted to thermal gravimetric analysis at 750°C. in air end nitrogen atmospheres, The results are shown in the fol-" lowing Table. ) - 55 = BAD ORIGINAL . , : em .

0 1 ° a o : - bh . @ “0 by Mj O- oN on — 0 . . * : g ol nn 0 on — ol nN Nn La La

EP

0 = g®R| © 0 on + od . . . * nN un [ & wz] + + tn tn 00 gq

Or 4 on og] MN ao ~4 s hed ® . » ° o of 00 ” = ~ 08d MN © rl

RH

*

S . o

Rl +o 43 . : °g ol A ol © Co O ~ o| 4 03] Ce . ¢ *

Oo ~~ on ol ~ : 3 Od ot — —t og uw =] odo £ A = nN MN — o os * * o * wl fy wn od 0 ol + ~ oN

Ro ) ~~ ~~ ’ 0 0 ~~ Land o © 0 0 ° » & 3 Qo . Q ~~’ ~~ ° : . oF = © ~ ~ © Fr) o © Q @Q +» + + + © ~~ o o ©

Oo Ww 0 8 a8 © og ~~ ho oO = |] O ~~ Uh Oo 0 st 2 2% “ow os of > ~ WIN n 80 tn : fo ~~ s DDN ee > » #| +O 0 no ot Pm PO er He 2 oe w OO 00 00 0 Oo 9] a Zon Ih Ih

Bl 9. Tol S08 Bol 9 2) LEG hod AY oO MIA MDE MOE AES oo BAD ORIGINAL. .

: The formate ester behaved in the expected mammer } yielding mainly 11gC0, and Ca0 as ashed residue when py- rolized in air. The acetate ester with Cal0 gave similar carbon yields in air and nitrogen, indicating better re- : sistance to oxidetion. This factor is of great impor~ tance in the application of the invention to the mam- facture of refractories, bonded carbon electrodes, eter ! A mix was prepared using: 85 g magnesia g graphite : 10 g Product IVb (acetate ester) _ and pressed into a cylindrical brick shape at 2 4/inch’e | " .

The resultant shape was allowed to cure at room tempera- . oo : ture for 24 hours then stage post-cured in sn oven for oo 15 66 hours at 100°C. followed by 24 hours at 150°C. The -~ samples were then heated in a muffle furnace at 850° Co ; So for 5 hours to yield a refractory materials

The samples were similar in appearance to bricks : made from a solution of novolek resin in ethylene glycol mixed with hexamine (hexamethylenetetrmmine) end heat cured. . The advantage of the phenolic resole esters of the ’ invention is that the brick in the unfired state is more . stable and stronger than one based on the novolak/glycol system. / i : Te - 57 = : oo BAD ORIGINAL ’

Application Example 5 = Foam

About 4.0 of the formate ester of Product C were mixed with 0.5 g of magnesium oxide, 0.1 g of , | surfactant DC193 (a commercially available product of . - 5 Dow Corning Corporation believed to comprise a siliw cone glycol polymer) and 1 g of Arcton II ("Arcton" is a registered Trademark) which is a commercially available chlorofluorocarbon blowing agent of ICI : Chemicals & Polymers Ltd). Finally, 0.5 g of water was added. An exothermic reaction occurred after about 30 seconds, the mixture creamed and foamed and soon after gelled. After standing, the foam was found te have a density of 200 kg/m, was strong and contained some closed cellse

Application Example 6 ~- Self-curing

A small cylindricel casting vas produced from the composition of Example 4 and left to cure for 6 weeks at 15~-20°¢C. It gave a compression strength of 9,900 pounds per square inch when tested on a Monsanto tensometer. The product exhibited good dimensional ) stability and is useful for casting application for which conventional acid-set phenolics are commonly usede / 58 = BAD ORIGINAL ee

Application Example 7 =~ Foundry Core Mix

About 30 g of Resin 1 (see Example 10 above) were mixed with 2000 g of dry Chelford 50 silica sand (where 50 is the AFS fineness number) at 18%c. in a high speed Kenwood Chef Mixer for 60 seconds. 9 g of a highly acetylated Product B ( this had been prepared according to the procedure set out for Product IVb above except that the reactants used were Product B (135 g), pyridine (22 ml) and acetic anhydride (270 g)) were added to the sand/Reesin 1 mixture and mixed for : . 45 seconds. The mix was then discharged and immediate- ly made into AFS compression test specimens using a standard rammer and precision tubes (The test specie ) ! mens are cylinders 2 inches in diameter and 2 inches oe 15 high, armed three times with a 1h pound weight drepped through 2 inches). They were then etored at 20° C./ 50% relative humidity and after hour and 24 hours, the compression strengths of the test specimens were mea-

CL oo sured as 1085 KNm~2 and 3945 KNm™2, respectively. . 2 Application Example 8 = Use as a Proppent Coating

Following generally the procedure for the pre- oo paration of Product C, a resin was prepared at a higher : viscosity than that of Product C, with the objective ' vo, / oT oC «59 = : : BAD ORIGINAL : . : —

of forming a resin that when cured, would have a melting point in the range of from 220°F. to 240°F. (104°C. to 116°C.). This resin was then converted to the acetate ester, and substantially dehydrated,

The resin ester was then mixed for about 30 minutes with sand in the proportion of about 2% by weight of the resin ester based on sand.

The product was sand coated with a binder that could be activated upon contact with an alkaline solu= tion. It is useful for enhancing the characteristice of a subterranean formation for the purpose, for exam- ple, of increasing its permeability and thus the pro- ductivity of a well situated in the subterranean formaw= tion,

In use, the coated sand is placed in or adja- cent to formation, and then caused to cure. Curing : is effected by passing into contact with the coated sand a solution of an appropriate basic material such as, for example, sodium hydroxide, calcium hydroxide, or the like. Instead of sand granules, the core of : the proppant may be a high compression material such as glass beads especially made for that purposes ! / oo 60 - dha

Claims (45)

WHAT 18 CLAIMED IS:

1. A method of making a cured phenolic resin composition which comprises reacting (1) an esterified phenolic compound containe . : 5 ing one or more phenolic hydroxyl groups and/or one or more esterified phenolic hye droxyl groups and further containing one or . more esterified methylol groups positioned ortho and/or para to a phenolic hydroxyl group or esterified phenolic hydroxyl group, (2) an unesterified phenolic resole resin com~ position, and (3) a base, in the presence of water and/or : other polar solvent, .

2. The method of Claim 1, wherein the esteri- : fied phenolic compound is a mononuclear phenol having an aromatic ring to which is attached at least one phenolic hydroxyl group, or an ester thereof contain. ing at least one esterified phenolic hydroxyl group which further contains one or more esterified methylel a groups attached to the aromatic ring at a position O ’ ortho and/or para to a phenolic hydroxyl group or ) esterified phenolic hydroxyl group.

3, The method of Claim 2, wherein the este rified phenolic compound is selected from the group consisting of esterified methylol~substituted phenol, o~cresol, m-cresol, p-cresol, 3¢5=xylen=l=ol, resorw . cinel, phloroglucinol, Bisphenol A, pyrogallol and mixtures thereof, and esters of these wherein the phenolic hydroxyl group or at least one of the phew nolic hydroxyl groups is ‘esterified. 4, The method of Claim 3, wherein the esteri= fied phenolic compound is selected from the group consisting of 2-acetyloxymethyl phenol, 2=methacryloy= loxymethyl phenol, 2-salicyloyloxymethyl phenol, 2= . acetyloxymethyl phenol acetate, 2,6~diacetyloxypethyl p~cresol, 2,6~diacetyloxymethyl p-cresol acetate, 2,4,6-triacetyloxymethyl phenol, 2,4,6=triacetyloxy~ methyl phenol acetate, 2,6~diacetyloxymethyl phenol acetate, 2,21,6,6'=tetraacetyloxymethyl Bisphenol A, ' : and 2,2',6,6'~tetraacetyloxymethyl Bisphenol A die acetate. :

. 20 5. The method of Claim 1, wherein the esteriw- - fied phenolic compound comprises an esterified me- thylol group~containing derivative of a condensation reaction product obtained by reacting two or more molecules of a mononuclear phenol with one or more

. molecules of a phenal~reactive aldehyde or ketone, wherein the said derivative contains eme or more : phenolic hydroxyl groups and/or one or more esteri- fied methylol groups positioned ortho and/or para to a phenolic hydroxyl group or esterified phenolie groupe

6. The method of Claim So wherein the esteriw . fied phenolic compound comprises an esterified mew thylol group-containing derivative of a condensation reaction product obtained by reading formaldehyde and a mononuclear phenol selected from the group consiste

RI. Ca 08 of phenol, Oy m-y oF p-cresaly 3,5=xylen-ol, Lo | : . wr i ers danger 0 pH RM at a pg RIG A RY resorcinol, phloroglucinel, pyrogallol and mixtures : So : | thereof, wherein the said derivative contains one or Co 15 more phenolic hydroxyl groups and/or one or more om . esterified phenolic hydroxyl groups and contalns one . } or more esterified methylol groups positioned ertho and/or para to a phenolic hydroxyl group or esteris } fied phenolic hydroxyl groupe ’ 20

7 The method of Claim 6, wherein the esteriw fied phenolic compound is an esterified or partially esterified phenol=formaldehyde resole resin. :

8, The method of Claim 7, wherein the esterie fied phenolic compound contains one or more acetyloxy= / : - 63 = BAD ORIGINAL methyl groups or formyloxyethyl groups positioned ortho and/or para to a phenolic hydroxyl group or esterified phenolic hydroxyl group.

9, The method of Claim 1, wherein the base is an alkali selected from the oxide and hydroxides of lithium, sodium, potassium, calcium and magnesium.

10. The method of making a cured phenolic resin composition which comprises reacting (1) an esteritied phenolic compound comprise + 10 ing an esterified methylol group~containing derivative of a condensation reaction pro- duct obtained by reacting two or more mole- cules of a mononuclear phenol with one or more molecules of a phenol-reactive aldehyde or ketone wherein the said derivative con- tains one or more phenolic hydroxyl groups and/or one or more esterified phenolic hy- droxyl groups and contains one or more esterified methylol groups positioned ortho and/or para to a phenolic hydroxyl group or esterified phenolic hydroxyl group, and ) (2) a base, in the presence of water and/or ¢ other polar solvent.

11. The method of Claim 10, wherein the esterified phenolic compound comprises an esterie fied methylol group-containing derivative of a conw densation reaction product obtained by reacting formaldehyde and ‘a mononuclear phenol selected from phenol, o-, mw or p-cresol, 345-xylen~l=0l, resor= cinol, phloroglucinol and pyrogallol, wherein the said derivative contains one or more phenolic hy=- : droxyl groups and/or one or more esterified phenolic hydroxyl groups and contains one or more esterified methylol groups positioned ortho andfor para to a phenolic hydroxyl group or esterified phenolic hy- droxyl groupe.

12. The method of Claim 11, wherein the . esterified phenolic compound is an esterified or oo 15 partially esterified phenol~-formaldehyde resol res " eine ! oo oo 13. The method of Claim 10, wherein the oo . esterified phenolic compound contains one or more acetyloxymethyl groups or formyloxymethyl groups .

Co. 20 pesitioned ortho and/er para to a phenolic hydroxyl | ' - group or esterified phenolic hydroxyl groups "14, The method of Claim 10, wherein the base ” js selected from the group consisting of calcium : SE oxide, calcium hydroxide, magnesium oxide and magnesium ‘

hydroxide.

15. The method of Claim 10, wherein a subs= tantially anhydrous base and a substantially anhy- drous esterified phenolic compound are mixed toge= ther to form a mixture which undergoes reaction to form a cured phenolic resin composition on the fur=- , ther treatment thereof with moisture,

16. The method of Claim 15, wherein a Bubs= tantially anhydrous homogeneous mixture of granular refractory material, base and esterified phenolic compound is prepared, shaped in a vented mould or core box and then steam or water vapor is passed into the shaped esterified phenolic compound 8o components of the mixture react to form a cured phenolic resin which binds the granular refractory materiale.

17. The method of Claim 15, wherein a subs— tantially anhydrous homogeneous mixture of base and ‘ esterified phenolic compound is applied, as a coating, on a substrate and the coated substrate is allowed to stand in a humid atmosphere for a period suffie cieht to enable the base and esterified phenolic compound to react in the presence of moisture to produce a cured phenolic resin composition.

18. The method of Claim 15, wherein a mix- - 66 w= ture of base, esterified phenolic compound and blowing agent is prepared, water is then added to : Co the mixture and the mixture then formed to produce a cured phenolic foams

19. The method of Claim 10, wherein a subse tantially anhydrous esterified phenolic compound is "mixed with granular refractory material and the re~ sulting mixture is then treated with an aqueous solution Te of the vase, whereupon the esterified phenolic compound and the base react together to form a cured phenolic resin composition which binds the granular refractory materiale .

20. A method of using a chemical precursor to : form a phenolic resin, wherein forming of said phenolis > 15 resin comprises reacting: (1) said chemical precursor; and (2) a base in the - presence of water and/or other : polar solvent, : oe wherein said chemical precursor is an esteri= N fied phenolic compound comprising an esterie fied methylol group-containing derivative . of a condensation reaction product obtained by reacting two or more molecules of a monow nuclear phenol with one or more molecules of a phenol~reactive aldehyde or ketone, wherein the said derivative contains one or more phenolic hydroxyl groups and/or one or more esterified phenolic hydroxyl : groups and contains one or more esterified phenolic hydroxyl groups and contains one or more esterified methylol groups posi= tioned ortho and/or para to a phenolic hye . droxyl groups or esterified phenolic hye droxyl groupe

21. The method of using of Claim 20, wherein the base is an alkaline earth metal compound selected from the group consisting of calcium oxide, calcium hydroxide, magnesium oxide and magnesium hydroxide.

22, The method of making a cured phenolic resin composition having reduced inorganic ion con- tent which comprises reacting. (1) an esterified phenolic compound comprising an esterified methylol group-containing derivative of a condensation reaction pro= duct obtained by reacting two or more mole~ cules of a mononuclear phenol with one or more molecules of a phenol-reactive alde= hyde or ketone, wherein the said deriva / o 68 «

tive contains one or more phenolic hy- droxyl groups and/or more esterified phe« nolic hydroxyl groups and contains one or more esterified methylol groups positioned ortho and/or para to a phenolic hydroxyl group or esterified phenolic hydroxyl group, and (2) a Mannich base. .

23+ The method of Claim 22, wherein the Man= nich base is 2,446~tris(dimethylaminomethyl)phenolo . ’ ’

a . BN

24, The method of Claim 22, wherein the esteriw : ne | | fied phenolic compound by fh Shenoinernel dehyde ToeLy heat ime itbanind Co resin at least partially acetylated or at least partiale Co L: Ch ly formulated. - 15

25. A derivative formed by esterifieation of Co : a condensantion reaction product wherein the conden= : sation reaction product is obtained vy reacting two : - : or more molecules of a mononuclear phenol selected from the group consisting of phenol, o-cresol, m= IN 20 cresol, p-cresol, 3,5=xylene-1-0l, resorcinol, phloroglucinol and pyrogallol with one or more molew cules of a phenol~reactive aldehyde or ketone and . wherein said derivative formed by the esterification . of said condensation reaction product contains one Co 25 or more esterified methylol groups attached ortho oo | "69 = BAD ORIGINAL and/or para to a phenolic hy droxyl group or esteri- fied methylol groups, whereon one or more of the esterified methylol groups contains a carboxylic acid ester group selected from the group consisting of formate, acetate, acetoncetate, acrylate, pro= . ' pionate, lactate, crotonate, methacrylate, butyrate, isobutyrate, caproate, caprylate, benzoate, toluate, p-aminobenzoate, cinnamate, laurate, myristate, oxa- late, succinate, fumarate, maleate, adipate, azelate, sebacate,, and groups of the formula 0 I -0C—( R \ oN (on) z wherein R is a saturated linear or branched lower hydrocarbyl groupy XxX = Qor ly y=21¢%03 and % =1 or 2, such that when x = 0, z =1, which derivative undergoes crosslinking on reaction with a base in the presence of water and/or other polar solvent.

26. A phenolic composition comprising / - 70 . : TCR RI Ep

} (1) an esterified phenolic compound containe : ing one or more phenolic hjdroxyl groups and/or one or more esterified phenolic hy= droxyl groups and further containing one oo or more esterified methylol groups posie tioned ortho and/or para to a phendlic hydroxyl group or esterified phenolic hy= . | droxyl group,

: . (2) an unesterified phenolic resole resin com- position, and : (3) a base, : wherein said phenolic composition undergoes reaction in the presence of water and/or other polar solvent to produce a cured phenolic resin composition. Co Ca | 15 8

27. The composition of Claim 26, wherein the : esterified phenolic compound is a mononuclear phenol oo : having an aromatic ring to which is attached at least J one phenolic hydroxyl group, or an ester thereof ' ; : containing at least one esterified phenolic hydroxyl group which further contains one or more esterified methylol groups attached to the aromatic ring at a position ortho and/or para to a phenolic hydroxyl group or esterified phenolic hydrosyl groupe oo

28. The composition of Claim 27, wherein the oa! Co / i oo - 7]

esterified phenolic compound is selected from the group consisting of esterified methylol-substituted phenol, o-cresol, m-cresol, p-cresol, 3,5~xylen-lw : ol, resorcinol, phloroglucinol, Bisphenol-A, pyro- gallol and mixtures thereof, and esters of these wherein the phenolic hydroxyl group or at least one of the phenolic hydroxyl groups is esterified.

29. The compoisiton of Claim 28, wherein the oo esterified phenolic compound is selected from the group consisting of 2-acetyloxymethyl phenol, 2-metha- cryloyloxymethyl phenol, 2-salicycloyloxymethyl phe- nol, 2-acetyloxymethyl phenol acetate, 2,6~diacetyl= oxymethyl pwresol, 2,6~diacetyloxymethyl p~cresol acetate, 2,6~diacetoacetyloxymethyl p-resol, 24k, 6m triacetyloxymethyl phenol, 2,4,6-~triacetyloxymethyl phenol acetate 2,6=diacetyloxymethyl phenol acetate 2,21,6,6'=tetraacetyloxymethyl Bisphenol A, and 2,2%,6,6 ~tetraacetyloxymethyl Bisphenol A diacetate,

30, The composition of Claim 26, wherein the esterified phenolic compound comprises an esterified methylol group-containing derivative of a condensa- tion reaction product obtained by reacting two or more molecules of a mononuclear phenol with one or more molecules of a phenol-reactive aldehyde or ketone, wherein the said derivative contains one or more phenolic hydroxyl groups and/or one or more : esterified methylol groups positioned ortho and/or para to a phenolic hydroxyl greup or esterified phenolic groupe. ’

31, The composition of Claim 30, wherein the : esterified phenolic compound derivative of a conden- sation reaction product obtained by reacting forme aldehyde and a mononunlear phenol selected from the group consisting of phenol, o0=, m= or p-cresol, 3, 5- , xylen-l-o0l, resorcinol, phloroglucinol, pyrogallol and mixtures thereof, wherein the said derivative contains one or more phenolic hydroxyl groups and/or one or more esterified phenolic hydroxyl groups posi= tioned ortho and/or para to a phenolic hydroxyl group or esterified phenolic hydroxyl groupe .

32, The composition of Claim 31, wherein the ' esterified phenolic compound is an esterified or : partially esterified phenol=formaldehyde resole resin.

33. A composition of Claim 30, wherein in esterified phenolic compound contains one or more acetyloxymethyl groups or formyloxymethyl groups positioned ortho and/or para te a phenolic hydroxyl . | group or esterified phenolic hydroxyl groupe Co Cy “73 =

: . . . 2 . ~~ 26581 - 34, A composition of Claim 26, wherein the . : base is an alkali selected from the group consisting of oxides and hydroxides of lithium, sodium, potas— sium, calcium and magnesium. 35, A phenolic resin composition comprising oo a mixture ofs ) no (1) an esterified phenolic compound comprising a derivative formed by esterifying the cone . densation reaction product obtained by rew acting two or more molecules of a monow- - nuclear phenol with on or more molecul es . of a phenol-reactive aldehyde or ketone, t wherein said derivative contains ome or Co more phenolic hydroxyl groups and/or more : 15 esterified phenolic hydroxyl groups and - , : contains one or more esterified methylol } groups positioned ortho and/or para to a phenolic hydroxyl group or esterified phenolic hydroxyl group, and : 20 (2) a base, ’ wherein said phenolic resin composition in the pree Co sence of water and/or other polar solvent undergoes } . reaction to produce a cured phenolic resin composie tion.

Lo on n 25 36. The composition of Claim 35, wherein IE - 7h

: i : + 26581 To ’ vo, , \ . } the esterified phenolic compound comprises an esteri- fied methylol group~containing derivative of a con- densation reaction product obtained by reacting form- . aldehyde and a mononuclear phenol selected from the group consisting of phenol, o-, m= or p-cresol, 3,5= / xylen=l-o0l, resorcinol phloroglucinol, pyrogallol or a'mixture thereof, wherein the said derivative con- tains one or more phenolic hydroxyl groups and/or . one or more esterified phemolic hydroxyl groups and contains one or more esterified methylol groups ’ positioned ortho and/or para to a phenolic hydroxyl group or esterified phenolic hydroxyl groupe.

37. The composition of Claim 36, wherein the . esterified phenolic cempound is an esterified or partially esterified phenol-formaldehyde resole . : resin. 38, The composition of Claim 37, wherein the esterified phenolic compound contains one or more acetyloxymethyl groups of formyloxymethyl groups positioned ortho and/or para to a phenolic hydroxyl : group or esterified phenolic hydroxyl group. . 39, The composition of Claim 35, wherein the

: .base is selected from the group consisting of cale cium oxide, calcium hydroxide, magnesium oxide and Co | -75 = '

v . 26581 . magnesium hydroxide. .

40. The composition of Claim 26, which addi- tionally contains a blowing or foaming agent.

41, The composition of Claim 35, which addi= tionally contains a blowing or foaming agent. :

42. A foundry moulding composition comprise ing a mixture of a major amount of granular refractory matee BN rial and a minor amount effective tc bind the granular res oon . fractory material of a phenolic resin composition of Claim " 10 26. :

43, A foundry moulding composition comprising a mixture of a major amount of granular refractory matem Co rial and a minor amount effective to bind the granular

I . } : . : refractory material of a phenolic resin composition of Claim 35. :

44. A composition of Claim 42 which additional ! ly contains a silane coupling agente.

45. A composition of Claim 43 which additional- 1y contains a silane coupling agent, , oo : PETER H.R.B. LEMON ‘ JAMES G. KING " ‘ GRAHAM MURRAY : HENRY LEONI ARTHUR H. GERBER C Inventors -